Post-synthetic annealing: linker self-exchange in UiO-66 and its effect on polymer-MOF interaction
File(s)
Accepted version
Author(s)
Type
Journal Article
Abstract
Post-synthetic exchange (PSE) and defect engineering have emerged as powerful techniques for tuning the properties and introducing novel functionality to metal organic frameworks (MOFs). Growing evidence suggests that each technique plays a key role in the mechanism of the other: linker coordination chemistry is pivotal to defective frameworks, while defect sites can help initiate PSE. Here, the intersection of these approaches is explored by exchanging an MOF with linkers already present within the framework. Post-synthetic annealing (PSA) modifies an MOF’s properties by redistributing the framework’s mixture of bound linker/modulator species. Using changes to the polymer-additive interactions in poly-1-trimethylsilyl-1-propyne nanocomposites observed through aging, we demonstrate that PSA causes one linker species to preferentially accumulate on the MOF’s crystal surface. Reaction conditions are shown to affect molecular composition of the resulting annealed UiO-66 MOFs, a finding explained through established reaction constants. This work simultaneously reveals intricacies of post-synthetic modification chemistry and presents a facile means of tuning MOFs and MOF nanocomposites.
Date Issued
2017-07-03
Date Acceptance
2017-07-03
Citation
Crystal Growth & Design, 2017, 17 (8), pp.4384-4392
ISSN
1528-7505
Publisher
American Chemical Society
Start Page
4384
End Page
4392
Journal / Book Title
Crystal Growth & Design
Volume
17
Issue
8
Copyright Statement
© 2017 American Chemical Society
Subjects
0306 Physical Chemistry (Incl. Structural)
0912 Materials Engineering
0302 Inorganic Chemistry
Inorganic & Nuclear Chemistry
Publication Status
Published